Hydroxylated polyamines and their use in dyeing with vat and sulphur dyestuffs



Patented Apr. 18 1939 UNITED STATES PATENT OFFICE HYDROXYLATED POLYAMINES AND THEIR USE IN DYEING WITH VAT AND SULPHUR DYESTUFFS Valentin Kartaschofl and Jakob Link, Basel, Switzerland, assignors to the firm Chemical Works Formerly Sandoz, Basel, Switzerland in Drawing. Application June 8, 1937, Serial No. 147,148. In Switzerland June 15, 1936 12 Claims.

The present invention relates to a process of dyeing and stripping vat and sulphur dyestuffs.

It is known that it is generally difficult to produce light shades with. vat and sulphur dyestuffs,

because the leuko compounds of these dyestuffs I or stripping baths of small quantities of such aliphatic polyamines that contain one orseveral free hydroxy groups in their molecule, allow to obtain level shades with vat and sulphur dyestuffs on cellulosic material or to strip oii and to level faulty unlevel dyeings with vat dyestuffs, because the leuko compounds of these dyestuifs are then transformed into a very finely dispersed form and their aflinity thus becomes modified.

The hydroxylated polyamines, when added in quantities of 0.01 to 2.0 parts per litre to the dyebath containing vat dyestufis, act as very effective levelling agents in the dyeing of yarn and piece goods, dyed in the jig, and of warp beams and cross wound bobbins dyed in the circulating dyemachine. They promote aflne dispersion and consequently a slow, but uniform and level exhaustion of the dyestufis. In addition they enable the dyer to produce complete and level penetration of warp beams and cross wound bobbins,

tions of dyestufi are obtained, when the dye bath is allowed to stand for a certain time.

As hydroxylated polyamines which are especially suitable forthe present process, there may be mentioned forexample the high molecular condensation products of glycerinedihalogenhy drines with primary, secondary or tertiary organic bases or ammonia. Also their N-alkyl and N- acyl derivatives can be used for this purpose. Further the hydroxyalkylated polyethylenepolyamines which can be obtained by treating for instance triethylene tetramine, tetraethle'nepentamine and their higher boiling homologues, with for example glycol or glycerine halogen hydrines or with ethylene oxide.

\ violet shade.

In dyeing with sulphur colors, the above mentioned compounds act very advantageously as they allow to obtain level dyeings with improved fastness to rubbing and to avoid glance in dark shades.

The object of the present invention is, therefore, a process for dyeing and stripping vat and sulphur dyestuffs, consisting in adding to the' dyeand stripping baths small quantities of hydroxylated aliphatic polyamines.

The following examples, without being limitative, illustrate the present invention, the parts being by weight:

Example 1 100 parts of a cotton tissue (mercerized poplin) which generally gives uneven dyeings in light shades, are dyed in the usual manner in 3000 parts of a dye-bath containing 48 volume-parts of caustic soda lye of 30 B.. 6 parts 'of hydrosulphite, 0.1 part of Sandothrenviolet N2R and 0.75 part of a polyamine prepared by condensing one molecule of a:v-glycerinedicl'rlorhydrine with two molecules of ammonia. The tissue dyed in this manner shows a clear and perfectly level If one dyes in the same manner, but in absence of the polyamine, an'unlevel striped dyeing will be obtained.

The above cited polyamine can be replaced with the same success by the polyamines obtained by treating polyethylenepolyamines with :27- glycerinedichlorhydrine at 105-108 C., or by a polyamine which can be prepared by treating with a:'y-glycerinedichlorhydrine the condensation product obtained-from one molecule of a27- glycerinedichlorhydrine and two molecules 01' ammonia.

Emample 2 Example 3 5 parts of cotton yarn are dyed in the usual manner in a dye bath containing per liter 0.6 part of Thional Dark Blue G and 0.25 part of a condensation product from a mixture of polyethylenepolyamines boiling point above 190 C. and a:'y-glycerinedichlorhydrine. A level dyeing fast to rubbing will be obtained.

Example 4 A piece of mercerized poplin is dyed in the usual manner in a dye bath containing per liter 0.2 part of Sandothrenorange NG and 0.15 part of a condensation product prepared by condensing two molecules of trimethylamine with one molecule of a:'y-glycerinedichlorhydrine in an autoclave at 140-150 C. A level dyeing will be obtained.

Example 5 100 parts of mercerized cotton in form of cross wound bobbins are dyed in a circulating dye-machine with a dye liquor containing 0.5 part of Sandothren Blue NRSC and 0.2 part of a polyamine prepared by first condensing 61 parts of monoethanolamine with 65 parts of az'y-glycerinedichlorhydrine and treating the condensation product thus obtained in presence of 80 parts of sodium hydroxide with 130 parts of glycerinedichlorhydrine at 120-130 C. The cops dyed in this manner are thoroughly dyed in a completely level shade.

Example 6 A piece of mercerized cotton tissue is dyed in the usual manner in a dye bath containing 1% of Sandothren Brown G (calculated on the weight of the tissue) and 0.1 part perliter bath of a condensation product prepared from one molecule of a:' -glycerinedichlorhydrine and two molecules of ammonia, and subsequently treated with an excess of dimethylsulphate in order to obtain a polyammonium base still containing free hydroxy groups. The dyeing thus obtained is quite level.

The above cited polyamine can also be replaced by the condensation product obtained by treating with ethylenechloride the polyamine obtained from one molecule of a:' -glycerinedichlorhydrine and two molecules of ammonia.

What we claim is:

1. The hydroxylated polyamines, prepared by treating the high molecular condensation products of a:- -glycerinedihalogenhydrine with a nitrogenous compound selected from the class consisting of ammonia, lower alkyl and hydroxyalkyl amines with an aliphatic dihalogenide selected from the group consisting of glycerinedihalogenhydrine and ethylenechloride, which are levelling and stripping assistants for vat and sulphur dyestuffs.

2. The hydroxylated polyamine, prepared by treating with u:y-glycerinedichlorhydrine the high molecular condensation product obtained from one molecule of a:' -glycerinedichlorhydrine and two molecules of ammonia, which is a levelling and stripping assistant for vat and sulphur dyestufis.

3. The hydroxylated polyamine, prepared by treating with ethylenechloride the high molecular condensation product obtained from one molecule of a:v-glycerinedichlorhydrine and two molecules of ammonia which is a levelling and stripping assistant for vat and sulphur dyestufis.

4. The hydroxylated polyamine, prepared by treating with one molecule of aw-glycerinedichlorhydrine the high molecular condensation product obtained from one molecule of monoethanolamine and one half molecule of a17- glycerinedichlorhydrine, which is a levelling and stripping assistant for vat and sulphur dyestuffs.

5. A process for dyeing vat and sulphur dyestufis on cellulosic material, comprising dyeing vat and sulphur dyestufis in a bath containing 0.01 to 2.0 parts per liter bath of a hydroxylated polyamine prepared by treating the high molecu-- lar condensation product of a,' -glycerinedichlo'r hydrine with a nitrogenous compound selected from the class consisting of ammonia, lower alkyl and hydroxyalkyl amines, with an aliphatic dihalogenide selected from the class consisting of a,'y-glycerinedihalogenhydrine and ethylenechlo-- ride.

6. A process for dyeing vat and sulphur dyestuffs on cellulosic material, comprising dyeing vat and sulphur dyestuffs in a bath containing 0.01 to 2.0 parts per liter bath of a hydroxylated polyamine prepared by treating with -glycerinedichlorhydrine the high molecular condensation product obtained from one molecule of a,'y-glycerinedichlorhydrine and two molecules of polyamine prepared by treating with one moler.

cule of a, -glycerinedichlorhydrine the high molecular condensation product obtained from one molecule of monoethanolamine and one half molecule of a, -glycerinedichlorhydrine;

'9. Dyeing liquors for vat and sulphur dyestufis, containing 0.01 to 2.0 parts per liter bath of a hydroxylated polyamine prepared by treating the high molecular condensation product of owy-g'lYC- erinediohlorhydrine with a nitrogenous compound selected from the class consisting of ammonia, lower alkyl and hydroxyalkyl amines, with an aliphatic dihalogenide selected from the class consisting of a,'y-glycerinedihalogenhydrine and ethylenechloride.

10. Dyeing liquors for vat and sulphur dyestuffs, containing 0.01 to 2.0 parts per liter bath of a hydroxylated polyamine prepared by treating with a,y-glycerinedichlorhydrine the high mo-- lecular condensation product obtained from one molecule of a,'y-glycerinedichlorhydrine and two molecules of ammonia.

11. Dyeing liquors for vat and sulphur dyestuffs, containing 0.01 to 2.0 parts per liter bath of a hydroxylated polyamine prepared by treating with ethylenechloride the high molecular condensation product obtained from one molecule of a,y-glycerinedichlorhydrine and two molecules of ammonia.

12. Dyeing liquors for vat and sulphur dyestuffs, containing 0.01 to 2.0 parts per liter bath of a hydroxylated polyamine prepared by treating with one molecule of a,'y-glycerinedichlorhydrine the high molecular condensation product obtained from one molecule of monoethanolamine and one half molecule of a,'y-glycerinedichlorhydrine.

VALENTIN KARTASCHOFF. JAKOB LINK. 

